WO2014010970A1 - High density anode active material and preparation method thereof - Google Patents

High density anode active material and preparation method thereof Download PDF

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WO2014010970A1
WO2014010970A1 PCT/KR2013/006216 KR2013006216W WO2014010970A1 WO 2014010970 A1 WO2014010970 A1 WO 2014010970A1 KR 2013006216 W KR2013006216 W KR 2013006216W WO 2014010970 A1 WO2014010970 A1 WO 2014010970A1
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metal oxide
lithium metal
oxide particles
negative electrode
active material
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PCT/KR2013/006216
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French (fr)
Korean (ko)
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오병훈
김제영
윤현웅
김예리
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주식회사 엘지화학
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Priority to JP2014527108A priority Critical patent/JP5888418B2/en
Priority to EP13806058.7A priority patent/EP2722914B1/en
Priority to CN201380002401.4A priority patent/CN103733394B/en
Priority to BR112014001839A priority patent/BR112014001839B8/en
Priority to US14/012,347 priority patent/US9608260B2/en
Publication of WO2014010970A1 publication Critical patent/WO2014010970A1/en

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G1/00—Methods of preparing compounds of metals not covered by subclasses C01B, C01C, C01D, or C01F, in general
    • C01G1/02—Oxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D15/00—Lithium compounds
    • C01D15/02—Oxides; Hydroxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/003—Titanates
    • C01G23/005—Alkali titanates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0416—Methods of deposition of the material involving impregnation with a solution, dispersion, paste or dry powder
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0419—Methods of deposition of the material involving spraying
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/14—Pore volume
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a negative electrode active material including high density lithium metal oxide particles and a lithium secondary battery including the same. It also relates to a manufacturing method for manufacturing the same.
  • Lithium titanium oxide is a zero-strain material with extremely low structural changes during charge and discharge, and thus has excellent life characteristics, forms a relatively high voltage range, and does not generate dendrite. It is known to have a very good safety and stability.
  • the lithium titanium oxide described above has a limit that the content of the binder increases for the electrode configuration because the electrical conductivity is lower than that of the carbon material such as graphite, and the atomization is required to improve the charging speed.
  • An object of the present invention is to provide a negative electrode active material comprising lithium metal oxide particles having a specific internal porosity and average particle diameter. Furthermore, to provide a secondary battery including the negative electrode active material.
  • Another object of the present invention is to provide a method for producing the lithium metal oxide particles.
  • lithium metal oxide particles, the internal porosity of the lithium metal oxide particles is 3% to 8%, characterized in that the average particle diameter (D 50 ) is 5 ⁇ m to 12 ⁇ m It provides a negative electrode active material.
  • a lithium salt and a metal oxide to a volatile solvent to prepare a precursor solution, supplying the precursor solution into the chamber of the spray drying equipment, the precursor solution
  • a method for producing lithium metal oxide particles having an internal porosity of 3% to 8% and an average particle diameter (D 50 ) of 5 ⁇ m to 12 ⁇ m including spraying and drying in a chamber.
  • a negative electrode including the negative electrode active material is provided.
  • a secondary battery including the negative electrode is provided.
  • the negative electrode active material according to the technical concept of the present invention may include a high density lithium metal oxide particle, thereby greatly improving the negative electrode adhesive force. This, in turn, can significantly reduce the amount of binder required to exert an electrode adhesive force of the same strength as compared with a conventional negative electrode active material having a normal density.
  • the lithium metal oxide particles may be formed at a high density. For this reason, the amount of binder required in the production of the negative electrode slurry can be reduced, and furthermore, it is advantageous in mass production of secondary batteries.
  • This high-density negative electrode active material is derived from a unique manufacturing method according to one embodiment of the present invention.
  • FIG. 1 is a SEM photograph of Li 4 Ti 5 O 12 of Comparative Example 3.
  • FIG. 1 is a SEM photograph of Li 4 Ti 5 O 12 of Comparative Example 3.
  • An anode active material includes lithium metal oxide particles, the internal porosity of the lithium metal oxide particles is 3% to 8%, the average particle diameter (D 50 ) is characterized in that 5 ⁇ m to 12 ⁇ m It is done.
  • the amount of the binder required for the preparation of the negative electrode slurry using a small amount or the same amount of the negative electrode Adhesion can be greatly improved.
  • the average particle diameter of the lithium metal oxide particles further smaller, high rate characteristics of the secondary battery can be improved.
  • the lithium metal oxide particles according to the exemplary embodiment of the present invention are secondary particles in which two or more primary particles are aggregated, and may be porous particulates.
  • the lithium metal oxide particles When the lithium metal oxide particles are used as a negative electrode active material of a lithium secondary battery as primary particles, there is no problem of electrode adhesion, but there is a disadvantage in that high-speed charge and discharge characteristics are poor.
  • the primary particles may be manufactured to a smaller size of 300 nm or less, but in this case, due to the increase in specific surface area, problems in the anode slurry manufacturing process, for example, products due to the use of excess binder Problems such as an increase in cost and a decrease in electrical conductivity may occur. Therefore, in order to solve the problem of using such primary particles, the lithium metal oxide particles according to one embodiment of the present invention may be in the form of secondary particles in which two or more primary particles are aggregated.
  • the lithium metal oxide particles according to one embodiment of the present invention are high density secondary particles having a small internal porosity of 3% to 8%, use of a smaller amount of binder than conventional secondary particles, for example, a conventional binder Even 20% to 50% of the amount used is not only excellent in electrode adhesion but also excellent in high rate characteristics.
  • the internal porosity of the lithium metal oxide particles is less than 3%, there may be substantial difficulties in terms of manufacturing process in that the secondary particles are formed by aggregation of the primary particles, and when the internal porosity exceeds 8%
  • the effect of the present invention to use a small amount of the binder may be insignificant, such as an increase in the amount of binder required to maintain proper electrode adhesion, resulting in a decrease in conductivity and a decrease in capacity.
  • the internal porosity of the lithium metal oxide particles may be defined as follows:
  • the measurement of the internal porosity is not particularly limited, and according to an embodiment of the present invention, for example, it may be measured using BELSORP (BET equipment) of BEL JAPAN using an adsorbent gas such as nitrogen.
  • the specific surface area (BET) of the lithium metal oxide particles is preferably 2 m 2 / g to 8 m 2 / g.
  • the specific surface area of the lithium metal oxide particles may be measured by a Brunauer-Emmett-Teller (BET) method.
  • BET Brunauer-Emmett-Teller
  • it can be measured by BET 6-point method by nitrogen gas adsorption distribution method using a porosimetry analyzer (Bell Japan Inc, Belsorp-II mini).
  • the average particle diameter (D 50 ) of the lithium metal oxide particles may be 5 ⁇ m to 12 ⁇ m, and the average particle diameter of the primary particles constituting the lithium metal oxide particles may be 100 nm to 400 nm.
  • the average particle diameter (D 50 ) of the lithium metal oxide particles may be defined as the particle size at 50% of the particle size distribution.
  • the average particle diameter (D 50 ) of the lithium metal oxide particles according to an embodiment of the present invention may be measured using, for example, a laser diffraction method.
  • the laser diffraction method can measure the particle diameter of several mm from the submicron region, and high reproducibility and high resolution can be obtained.
  • lithium metal oxide particles have a low conductivity, so that the average particle diameter is advantageous for application to a fast charging cell, but in this case, as described above, a large amount of the electrode is required to maintain proper electrode adhesion due to an increase in specific surface area. It needs a binder. That is, when the average particle diameter of the lithium metal oxide particles is less than 5 ⁇ m, the amount of the binder for maintaining the desired electrode adhesion increases due to an increase in the specific surface area of the negative electrode active material, thereby causing problems such as a decrease in electrode conductivity. There is concern. On the other hand, when the average particle diameter of lithium metal oxide particle exceeds 12 micrometers, there exists a problem that a fast charging characteristic falls.
  • the high-density lithium metal oxide particles according to one embodiment of the present invention in the case of lithium metal oxide particles having an average particle diameter in the range of 5 ⁇ m to 12 ⁇ m, the amount of the binder for maintaining the electrode adhesion may be reduced, The area capable of directly reacting with Li ions is increased to improve the fast charging properties.
  • the average particle diameter of the primary particles is less than 100 nm, the porosity of the lithium metal oxide particles formed by the aggregation of the primary particles increases, there is a problem that the electrode adhesive force is lowered, when the average particle diameter of more than 400 nm, The moldability may deteriorate, and a problem may occur in which granulation is difficult to control.
  • the lithium metal oxide according to an embodiment of the present invention is a material capable of occluding and releasing lithium ions, and may be represented by a composition formula of Li x M y O z .
  • M is independently one selected from the group consisting of Ti, Sn, Cu, Pb, Sb, Zn, Fe, In, Al and Zr or two or more of these elements
  • x, y and z are oxidation numbers of M It depends on the (oxidation number).
  • the lithium metal oxide is preferably Li 4 Ti 5 O 12 , LiTi 2 O 4 , Li 2 TiO 3 and Li 2 Ti 3 O 7 may be any one selected from the group consisting of lithium titanium oxide or a mixture of two or more thereof.
  • the lithium metal oxide according to an embodiment of the present invention may be included in 50% by weight to 100% by weight relative to the weight of the entire negative electrode active material.
  • the content of the lithium metal oxide is 100% by weight based on the total weight of the negative electrode active material, it means a case in which the negative electrode active material is composed of only the lithium metal oxide.
  • the negative electrode active material is any one selected from the group consisting of carbon-based materials, transition metal oxides, Si-based, and Sn-based materials commonly used in the negative electrode active material in addition to the lithium metal oxide. It may further include two or more active materials, but is not limited to these kinds.
  • the present invention comprises the steps of preparing a precursor solution by adding and stirring the lithium salt and metal oxide in a volatile solvent, supplying the precursor solution into the chamber of the spray drying equipment, spraying the precursor solution in the chamber to dry
  • a method for producing lithium metal oxide particles having an internal porosity of 3% to 8% and an average particle diameter (D 50 ) of 5 ⁇ m to 12 ⁇ m including the step of doing the above.
  • the secondary particles of the lithium metal oxide particles may be formed by a separate granulation process after the production of the primary particles, but usually to produce the primary particles through a single process and At the same time it can be produced by a method for agglomerating the primary particles.
  • the spray drying method is mentioned, for example.
  • a method of manufacturing the negative electrode active material according to an embodiment of the present invention will be described by taking a spray drying method as an example.
  • the metal oxide may be titanium oxide.
  • lithium metal oxide particles having an internal porosity of 3% to 8% and an average particle diameter (D 50 ) of 5 ⁇ m to 12 ⁇ m lithium salt and titanium oxide are added and stirred in a volatile solvent. To prepare a precursor solution.
  • the precursor solution may be prepared by dissolving a lithium salt in the volatile solvent and then adding titanium oxide as a metal oxide while stirring.
  • the volatile solvent is not particularly limited as long as it is a solvent that can be easily volatilized at the spraying process temperature, but may be, for example, water, acetone, alcohol, or the like.
  • the lithium salt is a lithium source in the spray drying process for producing lithium metal oxide particles, may be any one selected from the group consisting of lithium hydroxide, lithium oxide and lithium carbonate or a mixture of two or more thereof.
  • the titanium oxide becomes a titanium source.
  • the manufacturing method according to an embodiment of the present invention may include supplying the precursor solution to the chamber provided in the spray drying equipment.
  • the spray drying equipment may be used spray drying equipment that is commonly used, for example, ultrasonic spray drying apparatus, air nozzle spray drying apparatus, ultrasonic nozzle spray drying apparatus, filter expansion droplet generator or electrostatic spray drying apparatus Etc. may be used, but is not limited thereto.
  • the feed rate of the precursor solution into the chamber may be from 10 ml / min to 1000 ml / min. If the feed rate is less than 10 ml / min, the average particle diameter of the agglomerated lithium metal oxide particles is small, there is a difficulty in forming a high density lithium metal oxide particles, if the feed rate exceeds 1000 ml / min lithium metal Since the average particle diameter of the oxide particles becomes coarse, it may be difficult to achieve desired high rate characteristics.
  • the manufacturing method according to an embodiment of the present invention may include the step of spraying the precursor solution in the chamber to dry.
  • the precursor solution can be sprayed through a disk rotating at high speed in the chamber, and spraying and drying can be done in the same chamber.
  • the spray drying conditions for example, the flow rate of the carrier gas, the residence time in the reactor and the internal pressure.
  • the internal porosity of the lithium metal oxide particles may be controlled by controlling the drying temperature, and the drying may be performed at a temperature of 20 ° C. to 300 ° C., but as low as possible for the densification of the lithium metal oxide particles. It is advantageous to proceed in.
  • the average particle diameter of the lithium metal oxide particles can be controlled by changing the concentration of solids in the precursor solution.
  • the prepared precursor is subjected to a heat treatment process for about 5 hours to 20 hours between about 700 °C to 850 °C in an air atmosphere or an oxygen atmosphere using a common firing furnace to produce a high density lithium metal oxide particles.
  • the present invention also provides a negative electrode including the negative electrode active material described above and a lithium secondary battery including the negative electrode.
  • the negative electrode may be prepared by applying a slurry prepared by mixing a negative electrode slurry including the negative electrode active material to a solvent such as NMP (N-methyl pyrrolidone) on a negative electrode current collector, followed by drying and rolling.
  • the negative electrode slurry may optionally include a conductive material, a binder, a filler, etc. in addition to the negative electrode active material.
  • the negative electrode current collector is not particularly limited as long as it has high conductivity without causing chemical change in the battery.
  • the negative electrode current collector may be formed on the surface of copper, stainless steel, aluminum, nickel, titanium, calcined carbon, copper, or stainless steel. Surface-treated with carbon, nickel, titanium, silver and the like, aluminum-cadmium alloy and the like can be used.
  • the negative electrode current collector may form fine concavities and convexities on the surface to reinforce the bonding strength of the negative electrode active material, and may be used in various forms such as a film, a sheet, a foil, a net, a porous body, a foam, and a nonwoven fabric.
  • the conductive material is typically added in an amount of 1 wt% to 30 wt% based on the total weight of the mixture including the negative electrode active material.
  • a conductive material is not particularly limited as long as it has conductivity without causing chemical change in the battery, and examples thereof include graphite such as natural graphite and artificial graphite; Carbon blacks such as carbon black, acetylene black, Ketjen black, channel black, furnace black, lamp black, and summer black; Conductive fibers such as carbon fibers and metal fibers; Metal powders such as carbon fluoride powder, aluminum powder and nickel powder; Conductive whiskeys such as zinc oxide and potassium titanate; Conductive metal oxides such as titanium oxide; Conductive materials such as polyphenylene derivatives and the like can be used.
  • the binder is a component that assists in bonding the active material and the conductive material to the current collector, and is generally added in an amount of 1 wt% to 30 wt% based on the total weight of the mixture including the negative electrode active material.
  • binders include polyvinylidene fluoride (PVdF), polyvinyl alcohol, carboxymethyl cellulose (CMC), starch, hydroxypropyl cellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoro Low ethylene, polyethylene, polypropylene, ethylene-propylene-diene terpolymer (EPDM), sulfonated EPDM, styrene butadiene rubber, fluorine rubber, various copolymers and the like.
  • PVdF polyvinylidene fluoride
  • CMC carboxymethyl cellulose
  • EPDM ethylene-propylene-diene terpolymer
  • EPDM sulfonated EPDM
  • the filler is optionally used as a component for inhibiting expansion of the negative electrode, and is not particularly limited as long as it is a fibrous material without causing chemical change in the battery.
  • the filler include olefinic polymers such as polyethylene and polypropylene; Fibrous materials, such as glass fiber and carbon fiber, are used.
  • the method of evenly applying the negative electrode slurry to the negative electrode current collector may be selected from known methods or performed by a new suitable method in consideration of the properties of the material.
  • the paste may be distributed over the current collector, and then uniformly dispersed using a doctor blade or the like.
  • a method of distributing and dispersing in one process may be used.
  • a method such as die casting, comma coating, screen printing, or the like may be used, or the current collector may be formed on a separate substrate and then pressed or laminated. It can also be bonded with.
  • the positive electrode is manufactured by, for example, applying a positive electrode slurry containing a positive electrode active material onto a positive electrode current collector and then drying the positive electrode slurry. If necessary, the positive electrode slurry may include components as described above.
  • a spinel lithium manganese composite oxide having LiNi x Mn 2-x O 4 (x 0.01-0.6) having a relatively high potential due to the high potential of the negative electrode active material as the positive electrode active material.
  • the battery case used in the present invention may be adopted that is commonly used in the art, there is no limitation on the appearance according to the use of the battery, for example, cylindrical, square, pouch type or coin using a can (coin) type and the like.
  • the lithium secondary battery according to the present invention may not only be used in a battery cell used as a power source for a small device, but also preferably used as a unit battery in a medium-large battery module including a plurality of battery cells.
  • Preferred examples of the medium and large devices include, but are not limited to, electric vehicles, hybrid electric vehicles, plug-in hybrid electric vehicles, power storage systems, and the like.
  • Example 1 Preparation of Li 4 Ti 5 O 12 having an average particle diameter of 5.4 ⁇ m and an internal porosity of 3.5%
  • LiOHH 2 O and TiO 2 (Anatase) was mixed at 4: 5 (molar ratio), and the mixture was dissolved in pure water and stirred. At this time, the proportion of the total solid material was defined as the solid content of the solution, and stirred at 30% to prepare a precursor solution.
  • the precursor solution was fed into a chamber of a spray drying equipment (EinSystems) and sprayed and dried in the chamber. In this case, the conditions of the spray drying is carried out at a drying temperature of 130 °C internal pressure -20 mbar, feed rate 30 ml / min and then fired at 800 °C the precursor obtained in the air at an average particle diameter of 5.4 ⁇ m, the internal porosity 3.5% Li 4 Ti 5 O 12 Negative electrode active material Got it.
  • Average particle size Laser Diffraction Method (Microtrac MT 3000)
  • the prepared slurry was coated on one surface of a copper current collector to a thickness of 65 ⁇ m, dried and rolled, and then punched to a predetermined size to prepare a negative electrode.
  • Ethylene carbonate (EC) and diethyl carbonate (DEC) were mixed in a volume ratio of 30:70, and LiPF 6 was added to the nonaqueous electrolyte solvent to prepare a 1M LiPF 6 nonaqueous electrolyte.
  • a lithium metal foil was used as a counter electrode, that is, a positive electrode, a polyolefin separator was interposed between both electrodes, and the electrolyte was injected to prepare a coin-type half cell.
  • a lithium secondary battery was manufactured in the same manner as in Example 5, except that Li 4 Ti 5 O 12 of Comparative Examples 1 to 5 described in Table 1 were used as the anode active material.
  • the lithium metal oxide anode active materials prepared in Comparative Example 3 and Example 1 were confirmed by SEM micrographs, respectively, and the results are shown in FIGS. 1 and 2, respectively.
  • the secondary particles are porous secondary particles having pores formed on the inside and the surface thereof due to aggregation of the primary particles. Can be. At this time, the black part inside the particle represents a void.
  • the second, the primary particles are agglomerated, and is composed of the secondary particles, and the average particle diameter of 5.4 ⁇ m, a SEM picture of the internal porosity of 3.5% of Li 4 Ti 5 O 12, Comparative Li 4 Ti 5 of Example 1 It can be seen visually that the composition is higher density than O 12 .
  • the adhesion to the negative electrode was measured using the negative electrode prepared during the manufacturing process of the lithium secondary battery of Examples 5 to 8 and Comparative Examples 6 to 10. Adhesion was measured by a commonly known 180 o peel test. The results are shown in Table 2 below.
  • charge and discharge densities were set to 0.1, 0.2, 0.5, 1, 0.2, 2, 0.2, 5, 0.2, and 10C, respectively. It proceeded sequentially. At this time, the charge end voltage was set to 1.0V, and the discharge end voltage was set to 2.5V.
  • the high rate characteristic is expressed as a percentage value of the capacity at 0.1C by measuring the capacity at 10C.
  • the electrolyte solution does not penetrate smoothly into the internal active material, which causes the high rate characteristics to deteriorate despite having a high adhesive force.
  • the negative electrode active material according to the technical concept of the present invention may include a high density lithium metal oxide particle, thereby greatly improving the negative electrode adhesive force. This, in turn, can significantly reduce the amount of binder required to exert an electrode adhesive force of the same strength as compared with a conventional negative electrode active material having a normal density.
  • the lithium metal oxide particles may be formed at a high density. For this reason, the amount of binder required in the production of the negative electrode slurry can be reduced, and furthermore, it is advantageous in mass production of secondary batteries.

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Abstract

An anode active material of the present invention can comprise a lithium metal oxide having an inner porosity of 3-8 % and an average diameter (D50) of 5-12 μm. According to the present invention, a small amount or the same amount of a binder is used by comprising the lithium metal oxide having a high density when it is necessary to prepare an anode slurry, thereby remarkably improving the adhesive strength of an anode. In addition, a high rate characteristic of a secondary battery can be improved by reducing the average diameter of the lithium metal oxide.

Description

고밀도 음극 활물질 및 이의 제조방법High Density Negative Electrode Active Material and Manufacturing Method Thereof
본 발명은 고밀도의 리튬 금속 산화물 입자를 포함하는 음극 활물질 및 이를 포함하는 리튬 이차 전지에 관한 것이다. 또한 이를 제조하기 위한 제조방법에 관한 것이다. The present invention relates to a negative electrode active material including high density lithium metal oxide particles and a lithium secondary battery including the same. It also relates to a manufacturing method for manufacturing the same.
화석연료의 고갈에 의한 에너지원의 가격 상승, 환경 오염의 관심이 증폭되며, 친환경 대체 에너지원에 대한 요구가 미래생활을 위한 필수 불가결한 요인이 되고 있다. 이에 원자력, 태양광, 풍력, 조력 등 다양한 전력 생산기술들에 대한 연구가 지속되고 있으며, 이렇게 생산된 에너지를 더욱 효율적으로 사용하기 위한 전력저장장치 또한 지대한 관심이 이어지고 있다.Increasing the price of energy sources due to the depletion of fossil fuels, interest in environmental pollution is increasing, and the demand for environmentally friendly alternative energy sources is becoming an indispensable factor for future life. Accordingly, researches on various power production technologies such as nuclear power, solar energy, wind power, tidal power, etc. continue, and power storage devices for more efficient use of the generated energy are also drawing attention.
특히, 리튬 이차 전지의 경우, 모바일 기기에 대한 기술 개발과 수요가 증가함에 따라 에너지원으로서의 수요가 급격히 증가하고 있고, 최근에는 전기자동차(EV), 하이브리드 전기자동차(HEV)의 동력원으로서의 사용이 실현화되고 있으며, 그리드(Grid)화를 통한 전력 보조전원 등의 용도로도 사용영역이 확대되고 있다.In particular, in the case of lithium secondary batteries, as the development and demand for mobile devices increases, the demand as an energy source is rapidly increasing, and in recent years, the use of electric vehicles (EVs) and hybrid electric vehicles (HEVs) as power sources has been realized. In addition, the use area is also being expanded for grid auxiliary.
종래의 리튬 이차 전지의 음극은 음극 활물질로 구조적, 전기적 성질을 유지하면서 가역적인 리튬이온의 삽입(intercalation) 및 탈리가 가능한 탄소계 화합물이 주로 사용되었으나, 최근에는 리튬 티타늄 산화물에 대한 연구가 많이 진행되고 있다. As the negative electrode of the conventional lithium secondary battery, a carbon-based compound capable of intercalation and desorption of lithium ions while maintaining structural and electrical properties as a negative electrode active material has been mainly used. Recently, many studies on lithium titanium oxide have been conducted. It is becoming.
리튬 티타늄 산화물은, 충방전 동안 구조적 변화가 극히 낮아 제로 변형률(zero-strain) 물질로 수명특성이 매우 우수하고, 상대적으로 높은 전압대를 형성하며, 수지상 결정(dendrite)의 발생이 없어, 안전성(safety) 및 안정성(stability)이 매우 우수한 물질로 알려져 있다.Lithium titanium oxide is a zero-strain material with extremely low structural changes during charge and discharge, and thus has excellent life characteristics, forms a relatively high voltage range, and does not generate dendrite. It is known to have a very good safety and stability.
그러나, 상기한 리튬 티타늄 산화물은, 전기 전도성이 흑연 등과 같은 탄소재에 비하여 떨어지고, 충전 속도 향상을 위하여 미립화가 요구되기 때문에 전극 구성을 위하여는 바인더의 함량이 증가한다는 한계가 있다. However, the lithium titanium oxide described above has a limit that the content of the binder increases for the electrode configuration because the electrical conductivity is lower than that of the carbon material such as graphite, and the atomization is required to improve the charging speed.
본 발명이 해결하고자 하는 과제는 특정한 내부 공극률 및 평균 입경을 갖는 리튬 금속 산화물 입자를 포함하는 음극 활물질을 제공함에 있다. 더 나아가, 상기 음극 활물질을 포함하는 이차 전지를 제공함에 있다. An object of the present invention is to provide a negative electrode active material comprising lithium metal oxide particles having a specific internal porosity and average particle diameter. Furthermore, to provide a secondary battery including the negative electrode active material.
또한, 본 발명이 해결하고자 하는 다른 과제는 상기 리튬 금속 산화물 입자의 제조 방법을 제공함에 있다. In addition, another object of the present invention is to provide a method for producing the lithium metal oxide particles.
본 발명이 해결하려는 과제는 이상에서 언급한 과제로 제한되지 않으며, 언급되지 않은 또 다른 과제들은 아래의 기재로부터 당업자에게 명확하게 이해될 수 있을 것이다.The problem to be solved by the present invention is not limited to the above-mentioned problem, another task that is not mentioned will be clearly understood by those skilled in the art from the following description.
본 발명의 일 실시예에 따르면, 리튬 금속 산화물 입자를 포함하고, 상기 리튬 금속 산화물 입자의 내부 공극률은 3 % 내지 8 %이고, 평균 입경(D50)은 5 ㎛ 내지 12 ㎛인 것을 특징으로 하는 음극 활물질을 제공한다. According to an embodiment of the present invention, lithium metal oxide particles, the internal porosity of the lithium metal oxide particles is 3% to 8%, characterized in that the average particle diameter (D 50 ) is 5 ㎛ to 12 ㎛ It provides a negative electrode active material.
또한, 본 발명의 일 실시예에 따르면, 리튬염 및 금속 산화물을 휘발성 용매에 첨가 및 교반하여 전구체 용액을 제조하는 단계, 상기 전구체 용액을 분무건조 장비의 챔버 내로 공급하는 단계, 상기 전구체 용액을 상기 챔버 내에서 분무하여 건조하는 단계를 포함하는, 내부 공극률이 3 % 내지 8 %이고, 평균 입경(D50)이 5 ㎛ 내지 12 ㎛인 리튬 금속 산화물 입자의 제조방법을 제공한다. In addition, according to an embodiment of the present invention, adding a lithium salt and a metal oxide to a volatile solvent to prepare a precursor solution, supplying the precursor solution into the chamber of the spray drying equipment, the precursor solution Provided is a method for producing lithium metal oxide particles having an internal porosity of 3% to 8% and an average particle diameter (D 50 ) of 5 μm to 12 μm, including spraying and drying in a chamber.
또한, 본 발명의 일 실시예에 따르면, 상기 음극 활물질을 포함하는 음극을 제공한다.In addition, according to an embodiment of the present invention, a negative electrode including the negative electrode active material is provided.
나아가, 본 발명의 일 실시예에 따르면, 상기 음극을 포함하는 이차 전지를 제공한다.Furthermore, according to an embodiment of the present invention, a secondary battery including the negative electrode is provided.
상술한 바와 같이 본 발명의 기술적 사상에 의한 음극 활물질은 고밀도의 리튬 금속 산화물 입자를 포함함으로써 음극 접착력이 크게 향상될 수 있다. 이는 곧, 통상의 밀도를 갖는 종래의 음극 활물질에 비하여, 동일한 강도의 전극 접착력을 발휘하는 데에 필요한 바인더의 양을 현격하게 줄일 수 있다. As described above, the negative electrode active material according to the technical concept of the present invention may include a high density lithium metal oxide particle, thereby greatly improving the negative electrode adhesive force. This, in turn, can significantly reduce the amount of binder required to exert an electrode adhesive force of the same strength as compared with a conventional negative electrode active material having a normal density.
즉, 리튬 금속 산화물 입자의 내부 공극률이 감소됨에 따라, 리튬 금속 산화물 입자가 고밀도로 형성될 수 있다. 이러한 이유로 음극 슬러리의 제조시 필요한 바인더의 양을 감소시킬 수 있고, 나아가 이차 전지의 양산에 있어서 유리하다. That is, as the internal porosity of the lithium metal oxide particles is reduced, the lithium metal oxide particles may be formed at a high density. For this reason, the amount of binder required in the production of the negative electrode slurry can be reduced, and furthermore, it is advantageous in mass production of secondary batteries.
한편, 고밀도의 리튬 금속 산화물, 및 이로 인한 양호한 전극 접착력의 구현이 가능하기 때문에, 리튬 금속 산화물 입자의 평균 입경을 더욱 작게 형성하는 것이 가능하며, 이로 인하여 이차 전지의 고율 특성이 개선될 수 있다. On the other hand, since it is possible to implement a high density lithium metal oxide, and thereby good electrode adhesion, it is possible to form a smaller average particle diameter of the lithium metal oxide particles, thereby improving the high-rate characteristics of the secondary battery.
이러한, 고밀도의 음극 활물질은 본 발명의 일 실시예에 의하는 특유한 제조방법으로부터 기인한 것이다. This high-density negative electrode active material is derived from a unique manufacturing method according to one embodiment of the present invention.
도 1은 비교예 3의 Li4Ti5O12의 SEM 사진이다. 1 is a SEM photograph of Li 4 Ti 5 O 12 of Comparative Example 3. FIG.
도 2는 본 발명의 일 실시예에 따르는 실시예 1의 고밀도화된 Li4Ti5O12의 SEM 사진이다 2 is a SEM photograph of densified Li 4 Ti 5 O 12 of Example 1 according to an embodiment of the present invention
첨부한 도면들을 참조하여 본 발명의 바람직한 실시예들을 상세히 설명하기로 한다. 그러나, 하기 실시예는 본 발명을 예시하기 위한 것이며, 본 발명의 범주가 그것에 의해 한정되는 것은 아니다.Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings. However, the following examples are intended to illustrate the present invention, and the scope of the present invention is not limited thereto.
본 발명의 일 실시예에 따르는 음극 활물질은 리튬 금속 산화물 입자를 포함하고, 상기 리튬 금속 산화물 입자의 내부 공극률은 3 % 내지 8 %이고, 평균 입경(D50)은 5 ㎛ 내지 12 ㎛인 것을 특징으로 한다.An anode active material according to an embodiment of the present invention includes lithium metal oxide particles, the internal porosity of the lithium metal oxide particles is 3% to 8%, the average particle diameter (D 50 ) is characterized in that 5 ㎛ to 12 ㎛ It is done.
본 발명의 일 실시예에 따르면, 상기 특정 내부 공극률 및 평균 입경(D50)을 갖는 고밀도의 리튬 금속 산화물 입자를 포함함으로써, 음극 슬러리의 제조시 필요한 바인더의 양을 적게 사용하거나 동일 양으로도 음극 접착력을 크게 향상시킬 수 있다. 또한, 리튬 금속 산화물 입자의 평균 입경을 더욱 작게 형성함으로써 이차 전지의 고율 특성을 향상시킬 수 있다. According to an embodiment of the present invention, by including the high density lithium metal oxide particles having the specific internal porosity and the average particle diameter (D 50 ), the amount of the binder required for the preparation of the negative electrode slurry using a small amount or the same amount of the negative electrode Adhesion can be greatly improved. In addition, by forming the average particle diameter of the lithium metal oxide particles further smaller, high rate characteristics of the secondary battery can be improved.
본 발명의 일 실시예에 따른 상기 리튬 금속 산화물 입자는 둘 이상의 일차 입자가 응집된 이차 입자로서, 다공질의 입자상일 수 있다. The lithium metal oxide particles according to the exemplary embodiment of the present invention are secondary particles in which two or more primary particles are aggregated, and may be porous particulates.
상기 리튬 금속 산화물 입자가 일차 입자로서 리튬 이차 전지의 음극 활물질로 사용되는 경우, 전극 접착력의 문제는 없으나, 고속 충방전 특성이 떨어진다는 단점이 있다. 이러한 단점을 극복하기 위하여 일차 입자의 크기를 더욱 작은 300 nm 이하로 제조할 수도 있으나, 이 경우에는 오히려 비표면적의 증가로 인하여 음극 슬러리 제조 공정시의 문제, 예를 들면 과량의 바인더 사용으로 인한 제품 원가의 증가, 전기 전도성의 저하 등의 문제가 발생할 수 있다. 따라서, 이러한 일차 입자를 사용하는 경우의 문제점을 해결하기 위하여 본 발명의 일 실시예에 따르는 리튬 금속 산화물 입자는 둘 이상의 일차 입자가 응집된 이차 입자 형태일 수 있다. When the lithium metal oxide particles are used as a negative electrode active material of a lithium secondary battery as primary particles, there is no problem of electrode adhesion, but there is a disadvantage in that high-speed charge and discharge characteristics are poor. In order to overcome these disadvantages, the primary particles may be manufactured to a smaller size of 300 nm or less, but in this case, due to the increase in specific surface area, problems in the anode slurry manufacturing process, for example, products due to the use of excess binder Problems such as an increase in cost and a decrease in electrical conductivity may occur. Therefore, in order to solve the problem of using such primary particles, the lithium metal oxide particles according to one embodiment of the present invention may be in the form of secondary particles in which two or more primary particles are aggregated.
통상적으로, 이러한 이차 입자는 다공질의 형상을 갖기 때문에 전극 접착력을 유지하기 위하여 많은 양의 바인더를 필요로 하고 다량의 바인더의 사용으로 인하여 전지 용량이 감소될 수 있다. Typically, since these secondary particles have a porous shape, a large amount of binder is required to maintain electrode adhesion and battery capacity can be reduced due to the use of a large amount of binder.
그러나, 본 발명의 일 실시예에 따르는 리튬 금속 산화물 입자는 내부 공극률이 3 % 내지 8 %로 작은 고밀도의 이차 입자이기 때문에, 종래의 이차 입자에 비하여 적은 양의 바인더 사용, 예를 들어 종래의 바인더 사용량의 20 % 내지 50 %까지 적게 사용하더라도 충분한 전극 접착력을 발휘할 뿐만 아니라 고율 특성에 있어서도 우수하다. However, since the lithium metal oxide particles according to one embodiment of the present invention are high density secondary particles having a small internal porosity of 3% to 8%, use of a smaller amount of binder than conventional secondary particles, for example, a conventional binder Even 20% to 50% of the amount used is not only excellent in electrode adhesion but also excellent in high rate characteristics.
상기 리튬 금속 산화물 입자의 내부 공극률이 3 % 미만인 경우에는, 상기 이차 입자가 일차 입자의 응집에 의하여 형성된다는 점에서 제조 공정면에서 실질적인 어려움이 있을 수 있고, 내부 공극률이 8 %를 초과하는 경우에는 적절한 전극 접착력을 유지하기 위하여 필요한 바인더의 양이 증가하여 도전성이 저하되고, 용량이 감소하는 등, 적은 양의 바인더를 사용하고자 하는 본 발명의 효과가 미미할 수 있다. When the internal porosity of the lithium metal oxide particles is less than 3%, there may be substantial difficulties in terms of manufacturing process in that the secondary particles are formed by aggregation of the primary particles, and when the internal porosity exceeds 8% The effect of the present invention to use a small amount of the binder may be insignificant, such as an increase in the amount of binder required to maintain proper electrode adhesion, resulting in a decrease in conductivity and a decrease in capacity.
본 발명의 일 실시예에 따르면, 상기 리튬 금속 산화물 입자의 내부 공극률은 아래와 같이 정의 할 수 있다:According to an embodiment of the present invention, the internal porosity of the lithium metal oxide particles may be defined as follows:
내부 공극률 = 단위 질량당 공극 부피 / (비체적 + 단위 질량 당 공극 부피)Internal porosity = pore volume per unit mass / (specific volume + pore volume per unit mass)
상기 내부 공극률의 측정은 특별히 한정되지 않으며, 본 발명의 일 실시예에 따라, 예를 들어 질소 등의 흡착 기체를 이용하여 BEL JAPAN사의 BELSORP (BET 장비)를 이용하여 측정할 수 있다. The measurement of the internal porosity is not particularly limited, and according to an embodiment of the present invention, for example, it may be measured using BELSORP (BET equipment) of BEL JAPAN using an adsorbent gas such as nitrogen.
이와 비슷한 취지에서, 상기 리튬 금속 산화물 입자의 비표면적(BET)은 2 m2/g 내지 8 m2/g 인 것이 바람직하다. In a similar sense, the specific surface area (BET) of the lithium metal oxide particles is preferably 2 m 2 / g to 8 m 2 / g.
본 발명의 일 실시예에 따르면, 상기 리튬 금속 산화물 입자의 비표면적은 BET(Brunauer-Emmett-Teller; BET)법으로 측정할 수 있다. 예를 들어, 기공분포 측정기(Porosimetry analyzer; Bell Japan Inc, Belsorp-II mini)를 사용하여 질소 가스 흡착 유통법에 의해 BET 6 점법으로 측정할 수 있다. According to an embodiment of the present invention, the specific surface area of the lithium metal oxide particles may be measured by a Brunauer-Emmett-Teller (BET) method. For example, it can be measured by BET 6-point method by nitrogen gas adsorption distribution method using a porosimetry analyzer (Bell Japan Inc, Belsorp-II mini).
한편, 상기 리튬 금속 산화물 입자의 평균 입경(D50)은 5 ㎛ 내지 12 ㎛일 수 있으며, 이를 구성하는 일차 입자의 평균 입경은 100 nm 내지 400 nm일 수 있다. Meanwhile, the average particle diameter (D 50 ) of the lithium metal oxide particles may be 5 μm to 12 μm, and the average particle diameter of the primary particles constituting the lithium metal oxide particles may be 100 nm to 400 nm.
본 발명에 있어서, 상기 리튬 금속 산화물 입자의 평균 입경(D50)은 입경 분포의 50% 기준에서의 입경으로 정의할 수 있다. 본 발명의 일 실시예에 따른 상기 리튬 금속 산화물 입자의 평균 입경(D50)은 예를 들어, 레이저 회절법(laser diffraction method)을 이용하여 측정할 수 있다. 상기 레이저 회절법은 일반적으로 서브미크론(submicron) 영역에서부터 수 mm 정도의 입경의 측정이 가능하며, 고 재현성 및 고 분해성의 결과를 얻을 수 있다. In the present invention, the average particle diameter (D 50 ) of the lithium metal oxide particles may be defined as the particle size at 50% of the particle size distribution. The average particle diameter (D 50 ) of the lithium metal oxide particles according to an embodiment of the present invention may be measured using, for example, a laser diffraction method. In general, the laser diffraction method can measure the particle diameter of several mm from the submicron region, and high reproducibility and high resolution can be obtained.
통상 리튬 금속 산화물 입자는 낮은 도전성을 갖고 있으므로 고속 충전용 셀에 적용하기 위하여는 평균 입경이 작은 것이 유리하지만, 이 경우 전술한 바와 마찬가지로 비표면적 증가로 인하여 적절한 전극 접착력을 유지하기 위하여는 많은 양의 바인더를 필요로 한다. 즉, 상기 리튬 금속 산화물 입자의 평균 입경이 5 ㎛ 미만인 경우에는 음극 활물질의 비표면적의 증가로 인하여 원하는 전극 접착력을 유지하기 위한 바인더의 양이 증가하고, 이로 인하여 전극 전도도의 저하와 같은 문제가 발생할 우려가 있다. 한편, 리튬 금속 산화물 입자의 평균 입경이 12 ㎛를 초과하는 경우에는 고속 충전 특성이 저하된다는 문제가 있다. 따라서, 본 발명의 일 실시예에 따르는 고밀도 리튬 금속 산화물 입자로서, 평균 입경이 5 ㎛ 내지 12 ㎛ 범위인 리튬 금속 산화물 입자인 경우에는 전극 접착력을 유지하기 위한 바인더의 양을 줄일 수 있을 뿐만 아니라, Li 이온과 직접 반응 가능한 면적이 증가하여 고속 충전 특성도 아울러 개선할 수 있는 것이다. In general, lithium metal oxide particles have a low conductivity, so that the average particle diameter is advantageous for application to a fast charging cell, but in this case, as described above, a large amount of the electrode is required to maintain proper electrode adhesion due to an increase in specific surface area. It needs a binder. That is, when the average particle diameter of the lithium metal oxide particles is less than 5 μm, the amount of the binder for maintaining the desired electrode adhesion increases due to an increase in the specific surface area of the negative electrode active material, thereby causing problems such as a decrease in electrode conductivity. There is concern. On the other hand, when the average particle diameter of lithium metal oxide particle exceeds 12 micrometers, there exists a problem that a fast charging characteristic falls. Therefore, as the high-density lithium metal oxide particles according to one embodiment of the present invention, in the case of lithium metal oxide particles having an average particle diameter in the range of 5 μm to 12 μm, the amount of the binder for maintaining the electrode adhesion may be reduced, The area capable of directly reacting with Li ions is increased to improve the fast charging properties.
한편, 상기 일차 입자의 평균 입경이 100 nm 미만인 경우, 일차 입자의 응집으로 형성되는 리튬 금속 산화물 입자의 공극률이 증가하여 전극 접착력이 저하되는 문제가 있으며, 400 nm 초과인 경우, 리튬 금속 산화물 입자의 성형성이 저하되고, 조립화를 제어하기가 곤란한 문제가 발생할 수 있다. On the other hand, when the average particle diameter of the primary particles is less than 100 nm, the porosity of the lithium metal oxide particles formed by the aggregation of the primary particles increases, there is a problem that the electrode adhesive force is lowered, when the average particle diameter of more than 400 nm, The moldability may deteriorate, and a problem may occur in which granulation is difficult to control.
본 발명의 일 실시예에 따른 상기 리튬 금속 산화물은 리튬 이온을 흡장 및 방출할 수 있는 물질로서, LixMyOz 의 조성식으로 표현될 수 있다. 여기서, M은 각각 독립적으로 Ti, Sn, Cu, Pb, Sb, Zn, Fe, In, Al 및 Zr로 이루어진 군에서 선택된 어느 하나 또는 이들 중 2 이상의 원소이고, x, y 및 z는 M의 산화수(oxidation number)에 따라 결정된다. The lithium metal oxide according to an embodiment of the present invention is a material capable of occluding and releasing lithium ions, and may be represented by a composition formula of Li x M y O z . Here, M is independently one selected from the group consisting of Ti, Sn, Cu, Pb, Sb, Zn, Fe, In, Al and Zr or two or more of these elements, x, y and z are oxidation numbers of M It depends on the (oxidation number).
본 발명의 일 실시예에 따르면, 이차 전지의 음극 활물질로서 요구되는 충방전 특성 및 수명 특성의 관점에서, 상기 리튬 금속 산화물은 바람직하게는 Li4Ti5O12, LiTi2O4, Li2TiO3 및 Li2Ti3O7로 이루어진 군으로부터 선택되는 어느 하나 또는 이들 중 2종 이상의 혼합물인 리튬 티타늄 산화물일 수 있다. According to one embodiment of the present invention, in view of the charge and discharge characteristics and life characteristics required as the negative electrode active material of the secondary battery, the lithium metal oxide is preferably Li 4 Ti 5 O 12 , LiTi 2 O 4 , Li 2 TiO 3 and Li 2 Ti 3 O 7 may be any one selected from the group consisting of lithium titanium oxide or a mixture of two or more thereof.
본 발명의 일 실시예에 따르는 상기 리튬 금속 산화물은 전체 음극 활물질의 중량 대비 50 중량% 내지 100 중량%로 포함되어 있을 수 있다. 리튬 금속 산화물의 함량이 전체 음극 활물질 중량 대비 100 중량% 인 경우는, 리튬 금속 산화물만으로 음극 활물질이 구성되어 있는 경우를 의미한다. The lithium metal oxide according to an embodiment of the present invention may be included in 50% by weight to 100% by weight relative to the weight of the entire negative electrode active material. When the content of the lithium metal oxide is 100% by weight based on the total weight of the negative electrode active material, it means a case in which the negative electrode active material is composed of only the lithium metal oxide.
본 발명의 일 실시예에 따른 이차 전지에서 상기 음극 활물질은 상기 리튬 금속 산화물 이외에 음극 활물질에 통상적으로 사용되는 탄소계 물질, 전이금속산화물, Si계 및 Sn계로 이루어진 군에서 선택되는 어느 하나 또는 이들 중 2종 이상의 활물질을 더 포함할 수 있으며, 이들 종류로 제한되는 것은 아니다.In the secondary battery according to an embodiment of the present invention, the negative electrode active material is any one selected from the group consisting of carbon-based materials, transition metal oxides, Si-based, and Sn-based materials commonly used in the negative electrode active material in addition to the lithium metal oxide. It may further include two or more active materials, but is not limited to these kinds.
또한, 본 발명은 리튬염 및 금속 산화물을 휘발성 용매에 첨가 및 교반하여 전구체 용액을 제조하는 단계, 상기 전구체 용액을 분무건조 장비의 챔버 내로 공급하는 단계, 상기 전구체 용액을 상기 챔버 내에서 분무하여 건조하는 단계를 포함하는, 내부 공극률이 3 % 내지 8 %이고, 평균 입경(D50)이 5 ㎛ 내지 12 ㎛인 리튬 금속 산화물 입자의 제조방법을 제공한다. In addition, the present invention comprises the steps of preparing a precursor solution by adding and stirring the lithium salt and metal oxide in a volatile solvent, supplying the precursor solution into the chamber of the spray drying equipment, spraying the precursor solution in the chamber to dry Provided is a method for producing lithium metal oxide particles having an internal porosity of 3% to 8% and an average particle diameter (D 50 ) of 5 μm to 12 μm, including the step of doing the above.
본 발명의 일 실시예에 따르면, 상기 리튬 금속 산화물 입자의 이차 입자는 일차 입자를 제조한 후에 별도의 조립화 공정에 의하여 형성될 수 있지만, 통상적으로는 하나의 공정을 통하여 일차 입자를 생성함과 동시에 상기 일차 입자를 응집시키는 방법에 의하여 제조될 수 있다. 이러한 방법으로서, 예를 들면 분무건조법을 들 수 있다. 이하에서는 본 발명의 일 실시예에 따르는 음극 활물질의 제조방법을 분무건조법을 예로 들어서 설명한다. According to one embodiment of the present invention, the secondary particles of the lithium metal oxide particles may be formed by a separate granulation process after the production of the primary particles, but usually to produce the primary particles through a single process and At the same time it can be produced by a method for agglomerating the primary particles. As such a method, the spray drying method is mentioned, for example. Hereinafter, a method of manufacturing the negative electrode active material according to an embodiment of the present invention will be described by taking a spray drying method as an example.
본 발명의 일 실시예에 따르면, 상기 금속 산화물은 산화 티탄일 수 있다. According to an embodiment of the present invention, the metal oxide may be titanium oxide.
구체적으로 살펴보면, 본 발명의 내부 공극률이 3 % 내지 8 %이고, 평균 입경(D50)이 5 ㎛ 내지 12 ㎛인 리튬 금속 산화물 입자의 제조방법은 리튬염 및 산화 티탄을 휘발성 용매에 첨가 및 교반하여 전구체 용액을 제조하는 단계를 포함할 수 있다. Specifically, in the method of preparing lithium metal oxide particles having an internal porosity of 3% to 8% and an average particle diameter (D 50 ) of 5 μm to 12 μm, lithium salt and titanium oxide are added and stirred in a volatile solvent. To prepare a precursor solution.
보다 구체적으로, 상기 전구체 용액는 상기 휘발성 용매에 리튬염을 용해한 후, 교반하면서 금속 산화물인 산화 티탄을 첨가하여 제조될 수 있다. More specifically, the precursor solution may be prepared by dissolving a lithium salt in the volatile solvent and then adding titanium oxide as a metal oxide while stirring.
여기서, 상기 휘발성 용매는 분무공정 온도에서 쉽게 휘발할 수 있는 용매라면 특별히 제한되는 것은 아니지만, 예를 들면 물, 아세톤, 알코올 등일 수 있다. Here, the volatile solvent is not particularly limited as long as it is a solvent that can be easily volatilized at the spraying process temperature, but may be, for example, water, acetone, alcohol, or the like.
또한, 상기 리튬염은 리튬 금속 산화물 입자를 제조하기 위한 분무건조 공정에 있어서 리튬 소스가 되며, 수산화 리튬, 산화 리튬 및 탄산 리튬으로 이루어진 군에서 선택된 어느 하나 또는 이들 중 2종 이상의 혼합물일 수 있다. 나아가, 상기 산화 티탄은 티타늄 소스가 된다. In addition, the lithium salt is a lithium source in the spray drying process for producing lithium metal oxide particles, may be any one selected from the group consisting of lithium hydroxide, lithium oxide and lithium carbonate or a mixture of two or more thereof. Furthermore, the titanium oxide becomes a titanium source.
한편, 본 발명의 일 실시예에 따르는 제조방법은 상기 전구체 용액을 분무건조 장비에 구비된 챔버에 공급하는 단계를 포함할 수 있다. On the other hand, the manufacturing method according to an embodiment of the present invention may include supplying the precursor solution to the chamber provided in the spray drying equipment.
상기 분무건조 장비로는 통상 적으로 사용되는 분무건조 장비를 이용할 수 있으며, 예를 들어, 초음파 분무건조 장치, 공기노즐 분무건조 장치, 초음파노즐 분무건조 장치, 필터 팽창 액적 발생장치 또는 정전분무건조 장치 등이 사용될 수 있으나, 이에 한정되는 것은 아니다.The spray drying equipment may be used spray drying equipment that is commonly used, for example, ultrasonic spray drying apparatus, air nozzle spray drying apparatus, ultrasonic nozzle spray drying apparatus, filter expansion droplet generator or electrostatic spray drying apparatus Etc. may be used, but is not limited thereto.
본 발명의 일 실시예에 따르면, 상기 챔버 내로의 상기 전구체 용액의 공급 속도는 10 ㎖/분 내지 1000 ㎖/분일 수 있다. 만일 상기 공급 속도가 10 ㎖/분 미만인 경우에는 응집된 리튬 금속 산화물 입자의 평균 입경이 작아져 고밀도 리튬 금속 산화물 입자 형성의 어려움이 있으며, 상기 공급 속도가 1000 ㎖/분을 초과하는 경우에는 리튬 금속 산화물 입자의 평균 입경이 조대해지기 때문에 원하는 고율 특성을 구현하기 어려울 수 있다. According to one embodiment of the invention, the feed rate of the precursor solution into the chamber may be from 10 ml / min to 1000 ml / min. If the feed rate is less than 10 ml / min, the average particle diameter of the agglomerated lithium metal oxide particles is small, there is a difficulty in forming a high density lithium metal oxide particles, if the feed rate exceeds 1000 ml / min lithium metal Since the average particle diameter of the oxide particles becomes coarse, it may be difficult to achieve desired high rate characteristics.
나아가, 본 발명의 일 실시예에 따르는 제조방법은 상기 전구체 용액을 상기 챔버 내에서 분무하여 건조하는 단계를 포함할 수 있다. Furthermore, the manufacturing method according to an embodiment of the present invention may include the step of spraying the precursor solution in the chamber to dry.
상기 전구체 용액은 챔버 내에서 고속으로 회전하는 디스크를 통하여 분무될 수 있으며, 분무와 건조는 동일 챔버 내에서 이루어질 수 있다. The precursor solution can be sprayed through a disk rotating at high speed in the chamber, and spraying and drying can be done in the same chamber.
나아가, 본 발명의 내부 공극률의 구현을 위해서는 분무 건조 조건, 예를 들어, 운반기체의 유량, 반응기내 체류 시간 및 내부 압력 등의 제어를 통하여 가능할 수 있다. Furthermore, in order to realize the internal porosity of the present invention, it may be possible to control the spray drying conditions, for example, the flow rate of the carrier gas, the residence time in the reactor and the internal pressure.
본 발명의 일 실시예에 의해 건조 온도 조절을 통해 리튬 금속 산화물 입자의 내부 공극률을 제어할 수 있으며, 건조는 20 ℃ 내지 300 ℃의 온도에서 수행 가능하나 리튬 금속 산화물 입자의 고밀도화를 위해서는 가능한 낮은 온도에서 진행하는 것이 유리하다. According to an embodiment of the present invention, the internal porosity of the lithium metal oxide particles may be controlled by controlling the drying temperature, and the drying may be performed at a temperature of 20 ° C. to 300 ° C., but as low as possible for the densification of the lithium metal oxide particles. It is advantageous to proceed in.
또한 리튬 금속 산화물 입자의 평균 입경 조절을 위해서는 전구체 용액내 고형분의 농도 변경을 통해서 조절 가능하다.In addition, the average particle diameter of the lithium metal oxide particles can be controlled by changing the concentration of solids in the precursor solution.
상기 제조된 전구체는 일반적인 소성로를 사용하여 공기 분위기 또는 산소 분위기 하에서 약 700 ℃에서 850 ℃ 사이에서 약 5시간 내지 20시간 동안 열처리 공정을 진행하여 고밀도 리튬 금속 산화물 입자의 제조가 가능하다.The prepared precursor is subjected to a heat treatment process for about 5 hours to 20 hours between about 700 ℃ to 850 ℃ in an air atmosphere or an oxygen atmosphere using a common firing furnace to produce a high density lithium metal oxide particles.
본 발명은 또한, 상기한 음극 활물질을 포함하는 음극 및 상기 음극을 포함하는 리튬 이차 전지를 제공한다. The present invention also provides a negative electrode including the negative electrode active material described above and a lithium secondary battery including the negative electrode.
상기 음극은, 상기 음극 활물질을 포함하는 음극 슬러리를 NMP(N-메틸 피롤리돈) 등의 용매에 혼합하여 만들어진 슬러리를 음극 집전체 상에 도포한 후 건조 및 압연하여 제조될 수 있다. 상기 음극 슬러리는 상기 음극 활물질 이외에 선택적으로 도전재, 바인더, 충진제 등이 포함될 수 있다. The negative electrode may be prepared by applying a slurry prepared by mixing a negative electrode slurry including the negative electrode active material to a solvent such as NMP (N-methyl pyrrolidone) on a negative electrode current collector, followed by drying and rolling. The negative electrode slurry may optionally include a conductive material, a binder, a filler, etc. in addition to the negative electrode active material.
상기 음극 집전체는 전지에 화학적 변화를 유발하지 않으면서 높은 도전성을 가지는 것이라면 특별히 제한되는 것은 아니며, 예를 들어, 구리, 스테인리스 스틸, 알루미늄, 니켈, 티탄, 소성 탄소, 구리나 스테인리스 스틸의 표면에 카본, 니켈, 티탄, 은 등으로 표면처리한 것, 알루미늄-카드뮴 합금 등이 사용될 수 있다. 음극 집전체는, 표면에 미세한 요철을 형성하여 음극 활물질의 결합력을 강화시킬 수도 있으며, 필름, 시트, 호일, 네트, 다공질체, 발포체, 부직포체 등 다양한 형태로 사용될 수 있다.The negative electrode current collector is not particularly limited as long as it has high conductivity without causing chemical change in the battery. For example, the negative electrode current collector may be formed on the surface of copper, stainless steel, aluminum, nickel, titanium, calcined carbon, copper, or stainless steel. Surface-treated with carbon, nickel, titanium, silver and the like, aluminum-cadmium alloy and the like can be used. The negative electrode current collector may form fine concavities and convexities on the surface to reinforce the bonding strength of the negative electrode active material, and may be used in various forms such as a film, a sheet, a foil, a net, a porous body, a foam, and a nonwoven fabric.
상기 도전재는 통상적으로 음극 활물질을 포함한 혼합물 전체 중량을 기준으로 1 중량% 내지 30 중량%로 첨가된다. 이러한 도전재는 당해 전지에 화학적 변화를 유발하지 않으면서 도전성을 가진 것이라면 특별히 제한되는 것은 아니며, 예를 들어, 천연 흑연이나 인조 흑연 등의 흑연; 카본블랙, 아세틸렌 블랙, 케첸 블랙, 채널 블랙, 퍼네이스 블랙, 램프 블랙, 서머 블랙 등의 카본블랙; 탄소 섬유나 금속 섬유 등의 도전성 섬유; 불화 카본, 알루미늄, 니켈 분말 등의 금속 분말; 산화아연, 티탄산 칼륨 등의 도전성 위스키; 산화 티탄 등의 도전성 금속 산화물; 폴리페닐렌 유도체 등의 도전성 소재 등이 사용될 수 있다. The conductive material is typically added in an amount of 1 wt% to 30 wt% based on the total weight of the mixture including the negative electrode active material. Such a conductive material is not particularly limited as long as it has conductivity without causing chemical change in the battery, and examples thereof include graphite such as natural graphite and artificial graphite; Carbon blacks such as carbon black, acetylene black, Ketjen black, channel black, furnace black, lamp black, and summer black; Conductive fibers such as carbon fibers and metal fibers; Metal powders such as carbon fluoride powder, aluminum powder and nickel powder; Conductive whiskeys such as zinc oxide and potassium titanate; Conductive metal oxides such as titanium oxide; Conductive materials such as polyphenylene derivatives and the like can be used.
상기 바인더는 활물질과 도전재 등의 결합과 집전체에 대한 결합에 조력하는 성분으로서, 통상적으로 음극 활물질을 포함하는 혼합물 전체 중량을 기준으로 1 중량% 내지 30 중량%로 첨가된다. 이러한 바인더의 예로는, 폴리비닐리덴플루오라이드(PVdF), 폴리비닐알코올, 카르복시메틸셀룰로우즈(CMC), 전분, 히드록시프로필셀룰로우즈, 재생 셀룰로우즈, 폴리비닐피롤리돈, 테트라플루오로에틸렌, 폴리에틸렌, 폴리프로필렌, 에틸렌-프로필렌-디엔 테르 폴리머(EPDM), 술폰화 EPDM, 스티렌 부타디엔 고무, 불소 고무, 다양한 공중합제 등을 들 수 있다.The binder is a component that assists in bonding the active material and the conductive material to the current collector, and is generally added in an amount of 1 wt% to 30 wt% based on the total weight of the mixture including the negative electrode active material. Examples of such binders include polyvinylidene fluoride (PVdF), polyvinyl alcohol, carboxymethyl cellulose (CMC), starch, hydroxypropyl cellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoro Low ethylene, polyethylene, polypropylene, ethylene-propylene-diene terpolymer (EPDM), sulfonated EPDM, styrene butadiene rubber, fluorine rubber, various copolymers and the like.
상기 충진제는 음극의 팽창을 억제하는 성분으로서 선택적으로 사용되며, 당해 전지에 화학적 변화를 유발하지 않으면서 섬유상 재료라면 특별히 제한되는 것은 아니며, 예를 들어, 폴리에틸렌, 폴리프로필렌 등의 올리핀계 중합제; 유리섬유, 탄소섬유 등의 섬유상 물질이 사용된다.The filler is optionally used as a component for inhibiting expansion of the negative electrode, and is not particularly limited as long as it is a fibrous material without causing chemical change in the battery. Examples of the filler include olefinic polymers such as polyethylene and polypropylene; Fibrous materials, such as glass fiber and carbon fiber, are used.
음극 슬러리를 음극 집전체에 고르게 도포하는 방법은 재료의 특성 등을 감안하여 공지 방법 중에서 선택하거나 새로운 적절한 방법으로 행할 수 있다. 예를 들어, 페이스트를 집전체 위에 분배시킨 후 닥터 블레이드(doctor blade) 등을 사용하여 균일하게 분산시킬 수 있다. 경우에 따라서는, 분배와 분산 과정을 하나의 공정으로 실행하는 방법을 사용할 수도 있다. 이 밖에도, 다이 캐스팅(die casting), 콤마 코팅(comma coating), 스크린 프린팅(screen printing) 등의 방법을 택할 수도 있으며, 또는 별도의 기재(substrate) 위에 성형한 후 프레싱 또는 라미네이션 방법에 의해 집전체와 접합시킬 수도 있다. The method of evenly applying the negative electrode slurry to the negative electrode current collector may be selected from known methods or performed by a new suitable method in consideration of the properties of the material. For example, the paste may be distributed over the current collector, and then uniformly dispersed using a doctor blade or the like. In some cases, a method of distributing and dispersing in one process may be used. In addition, a method such as die casting, comma coating, screen printing, or the like may be used, or the current collector may be formed on a separate substrate and then pressed or laminated. It can also be bonded with.
상기 양극은, 예를 들어, 양극 집전체 상에 양극 활물질을 포함하고 있는 양극 슬러리를 도포한 후 건조하여 제조되며, 상기 양극 슬러리에는, 필요에 따라, 앞서 설명한 바와 같은 성분들이 포함될 수 있다.The positive electrode is manufactured by, for example, applying a positive electrode slurry containing a positive electrode active material onto a positive electrode current collector and then drying the positive electrode slurry. If necessary, the positive electrode slurry may include components as described above.
특히, 상기 리튬 이차 전지는 양극 활물질로서 리튬 코발트 산화물(LiCoO2), 리튬 니켈 산화물(LiNiO2) 등의 층상 화합물이나 1 또는 그 이상의 전이금속으로 치환된 화합물; 화학식 Li1+xMn2-xO4(여기서, x는 0 내지 0.33임), LiMnO3, LiMn2O3, LiMnO2 등의 리튬 망간 산화물; 리튬 동 산화물(Li2CuO2); LiV3O8, LiFe3O4, V2O5, Cu2V2O7 등의 바나듐 산화물; 화학식 LiNi1-xMxO2 (여기서, M = Co, Mn, Al, Cu, Fe, Mg, B 또는 Ga 이고, x = 0.01 내지 0.3임)으로 표현되는 Ni 사이트형 리튬 니켈 산화물; 화학식 LiMn2-xMxO2 (여기서, M = Co, Ni, Fe, Cr, Zn 또는 Ta 이고, x= 0.01 내지 0.1임) 또는 Li2Mn3MO8 (여기서, M = Fe, Co, Ni, Cu 또는 Zn임)으로 표현되는 리튬 망간 복합 산화물; 화학식의 Li 일부가 알칼리토금속 이온으로 치환된 LiMn2O4; 디설파이드 화합물; Fe2(MoO4)3 등을 사용할 수 있으나 바람직하게는 LiNixMn2-xO4(0.01=x=0.6)을 사용할 수 있고, 더욱 바람직하게는 LiNi0.5Mn1.5O4 또는 LiNi0.4Mn1.6O4을 사용할 수 있다. 즉, 본 발명에서, 음극 활물질의 높은 전위로 인하여 상대적으로 고전위를 가지는 LiNixMn2-xO4(x = 0.01 - 0.6임)의 스피넬 리튬 망간 복합 산화물을 양극 활물질로 사용하는 것이 바람직하다.In particular, the lithium secondary battery includes a layered compound such as lithium cobalt oxide (LiCoO 2 ), lithium nickel oxide (LiNiO 2 ), or a compound substituted with one or more transition metals as a positive electrode active material; Lithium manganese oxides such as Li 1 + x Mn 2-x O 4 (where x is 0 to 0.33), LiMnO 3 , LiMn 2 O 3 , LiMnO 2, and the like; Lithium copper oxide (Li 2 CuO 2 ); LiV 3 O 8, LiFe 3 O 4, V 2 O 5, vanadium oxide such as Cu 2 V 2 O 7; Ni-site type lithium nickel oxide represented by the formula LiNi 1-x M x O 2 , wherein M = Co, Mn, Al, Cu, Fe, Mg, B or Ga, and x = 0.01 to 0.3; Formula LiMn 2-x M x O 2 , wherein M = Co, Ni, Fe, Cr, Zn or Ta and x = 0.01 to 0.1, or Li 2 Mn 3 MO 8 , wherein M = Fe, Co, Lithium manganese composite oxide represented by Ni, Cu or Zn); LiMn 2 O 4 in which a part of Li in the formula is substituted with alkaline earth metal ions; Disulfide compounds; Fe 2 (MoO 4 ) 3 and the like can be used but preferably LiNi x Mn 2-x O 4 (0.01 = x = 0.6), more preferably LiNi 0.5 Mn 1.5 O 4 or LiNi 0.4 Mn 1.6 O 4 can be used. That is, in the present invention, it is preferable to use a spinel lithium manganese composite oxide having LiNi x Mn 2-x O 4 (x = 0.01-0.6) having a relatively high potential due to the high potential of the negative electrode active material as the positive electrode active material. .
본 발명에서 사용되는 전지 케이스는 당분야에서 통상적으로 사용되는 것이 채택될 수 있고, 전지의 용도에 따른 외형에 제한이 없으며, 예를 들면, 캔을 사용한 원통형, 각형, 파우치(pouch)형 또는 코인(coin)형 등이 될 수 있다.The battery case used in the present invention may be adopted that is commonly used in the art, there is no limitation on the appearance according to the use of the battery, for example, cylindrical, square, pouch type or coin using a can (coin) type and the like.
본 발명에 따른 리튬 이차 전지는 소형 디바이스의 전원으로 사용되는 전지셀에 사용될 수 있을 뿐만 아니라, 다수의 전지셀들을 포함하는 중대형 전지모듈에 단위전지로도 바람직하게 사용될 수 있다. 상기 중대형 디바이스의 바람직한 예로는 전기자동차, 하이브리드 전기자동차, 플러그-인 하이브리드 전기자동차, 전력 저장용 시스템 등을 들 수 있지만, 이들 만으로 한정되는 것은 아니다.The lithium secondary battery according to the present invention may not only be used in a battery cell used as a power source for a small device, but also preferably used as a unit battery in a medium-large battery module including a plurality of battery cells. Preferred examples of the medium and large devices include, but are not limited to, electric vehicles, hybrid electric vehicles, plug-in hybrid electric vehicles, power storage systems, and the like.
이하, 본 발명을 구체적으로 설명하기 위해 실시예를 들어 상세하게 설명하기로 한다. 그러나, 본 발명에 따른 실시예들은 여러가지 다른 형태로 변형될 수 있으며, 본 발명의 범위가 하기에서 상술하는 실시예들에 한정되는 것은 아니다. Hereinafter, the present invention will be described in detail with reference to Examples. However, embodiments according to the present invention can be modified in many different forms, the scope of the present invention is not limited to the embodiments described below.
실시예Example
실시예 1: 평균 입경이 5.4 ㎛이고, 내부 공극률이 3.5 %인 Li4Ti5O12의 제조Example 1: Preparation of Li 4 Ti 5 O 12 having an average particle diameter of 5.4 μm and an internal porosity of 3.5%
LiOHㆍH2O 및 TiO2 (아나타제)를 4:5(몰수비)로 혼합하고 이 혼합물을 순수물에 용해시킨 후 교반하였다. 이 때 전체 고체 물질의 비율을 용액의 고형분으로 정의하고 30%로 맞추어 교반하여 전구체 용액을 제조하였다. 상기 전구체 용액을 분무 건조장비(아인시스템 제품)의 챔버 내로 공급하고, 챔버 내에서 분무하여 건조하였다. 이때, 상기 분무 건조의 조건은 건조온도 130℃ 내부압력 -20 mbar, 공급속도 30 ml/분으로 진행한 뒤 얻어지는 전구체를 800℃에서 공기 중에 소성하여 평균 입경이 5.4 ㎛이고, 내부 공극률이 3.5 %인 Li4Ti5O12 음극 활물질을 얻었다.LiOHH2O and TiO2(Anatase) was mixed at 4: 5 (molar ratio), and the mixture was dissolved in pure water and stirred. At this time, the proportion of the total solid material was defined as the solid content of the solution, and stirred at 30% to prepare a precursor solution. The precursor solution was fed into a chamber of a spray drying equipment (EinSystems) and sprayed and dried in the chamber. In this case, the conditions of the spray drying is carried out at a drying temperature of 130 ℃ internal pressure -20 mbar, feed rate 30 ml / min and then fired at 800 ℃ the precursor obtained in the air at an average particle diameter of 5.4 ㎛, the internal porosity 3.5% Li4Ti5O12Negative electrode active material Got it.
실시예 2 내지 4 : Li4Ti5O12의 제조Examples 2 to 4: Preparation of Li 4 Ti 5 O 12
하기 표 1에 기재된 분무 조건을 변경한 것을 제외하고 실시예 1과 동일한 방법으로 표 1에 기재된 평균 입경 및 내부 공극률을 갖는 Li4Ti5O12 음극 활물질들을 얻었다.Li having an average particle diameter and internal porosity shown in Table 1 in the same manner as in Example 1 except that the spraying conditions shown in Table 1 were changed.4Ti5O12Anode active materials Got it.
비교예 1 내지 5 : Li4Ti5O12의 제조Comparative Examples 1 to 5: Preparation of Li 4 Ti 5 O 12
하기 표 1에 기재된 분무 조건을 변경한 것을 제외하고 실시예 1과 동일한 방법으로 표 1에 기재된 평균 입경 및 내부 공극률을 갖는 Li4Ti5O12 음극 활물질들을 얻었다.Li having an average particle diameter and internal porosity shown in Table 1 in the same manner as in Example 1 except that the spraying conditions shown in Table 1 were changed.4Ti5O12Anode active materials Got it.
표 1
예 건조온도 (℃) 내부압력(mbar) 용액 고형분( %) 공급속도 (ml/분) 1평균 입경(㎛) 2내부공극률(%)
실시예 1 130 -20 30 30 5.4 3.5
실시예 2 170 -30 30 30 6 4.1
실시예 3 210 -40 30 30 6.2 7.8
실시예 4 130 -20 40 70 12 3.6
비교예 1 80 -10 30 30 5.5 2.5
비교예 2 230 -50 30 30 6 9
비교예 3 250 -70 30 30 6.5 15
비교예 4 130 -20 10 10 3 3.5
비교예 5 130 -20 50 100 14 3.7
Table 1
Yes Drying temperature (℃) Internal pressure (mbar) Solution solids (%) Feed rate (ml / min) 1 Average particle size (㎛) 2 Internal porosity (%)
Example 1 130 -20 30 30 5.4 3.5
Example 2 170 -30 30 30 6 4.1
Example 3 210 -40 30 30 6.2 7.8
Example 4 130 -20 40 70 12 3.6
Comparative Example 1 80 -10 30 30 5.5 2.5
Comparative Example 2 230 -50 30 30 6 9
Comparative Example 3 250 -70 30 30 6.5 15
Comparative Example 4 130 -20 10 10 3 3.5
Comparative Example 5 130 -20 50 100 14 3.7
1. 평균 입경: 레이저 회절 입도법(Laser Diffraction Method :Microtrac MT 3000)1. Average particle size: Laser Diffraction Method (Microtrac MT 3000)
2. 내부공극률 = 단위 질량당 공극 부피 / (비체적 + 단위 질량 당 공극 부피)2. Internal porosity = pore volume per unit mass / (specific volume + pore volume per unit mass)
(BEL JAPAN 사의 BELSORP(BET 장비) 사용, 메조포어 측정법인 BJH법에 의해 계산된 값 사용)(Using BELSORP (BET equipment) of BEL JAPAN, using the value calculated by BJH method, mesopore measurement method)
실시예 5 내지 8 : 리튬 이차 전지의 제조Examples 5 to 8: Preparation of lithium secondary battery
<음극의 제조><Production of Cathode>
음극 활물질로서 상기 표 1에서 제조된 실시예 1 내지 4의 Li4Ti5O12, 도전재로 카본 블랙(Super P) 및 바인더로 폴리비닐리덴플루오라이드(PVdF)를 88:4:8의 중량비로 혼합하고, 이들을 용매인 N-메틸-2-피롤리돈에 혼합하여 슬러리를 제조하였다. 제조된 슬러리를 구리 집전체의 일면에 65 ㎛의 두께로 코팅하고, 건조 및 압연한 후 일정 크기로 펀칭(pouching)하여 음극을 제조하였다. Li 4 Ti 5 O 12 of Examples 1 to 4 prepared in Table 1 as the negative electrode active material, carbon black (Super P) as the conductive material and polyvinylidene fluoride (PVdF) as the binder, the weight ratio of 88: 4: 8 And mixed with N-methyl-2-pyrrolidone as a solvent to prepare a slurry. The prepared slurry was coated on one surface of a copper current collector to a thickness of 65 μm, dried and rolled, and then punched to a predetermined size to prepare a negative electrode.
<리튬 이차 전지의 제조><Production of Lithium Secondary Battery>
에틸렌 카보네이트(EC) 및 디에틸 카보네이트(DEC)를 30:70의 부피비로 혼합하고, 상기 비수전해액 용매에 LiPF6를 첨가하여 1M LiPF6 비수전해액을 제조하였다.Ethylene carbonate (EC) and diethyl carbonate (DEC) were mixed in a volume ratio of 30:70, and LiPF 6 was added to the nonaqueous electrolyte solvent to prepare a 1M LiPF 6 nonaqueous electrolyte.
또한, 상대전극, 즉 양극으로 리튬 금속 호일(foil)을 사용하며, 양 전극 사이에 폴리올레핀 분리막을 개재시킨 후, 상기 전해액을 주입하여 코인형 반쪽 전지를 제조하였다.Also, a lithium metal foil was used as a counter electrode, that is, a positive electrode, a polyolefin separator was interposed between both electrodes, and the electrolyte was injected to prepare a coin-type half cell.
비교예 6 내지 10 : 이차 전지의 제조Comparative Examples 6 to 10: Preparation of Secondary Battery
음극 활물질로 상기 표 1에 기재된 비교예 1 내지 5의 Li4Ti5O12를 사용한 것을 제외하고는 상기 실시예 5와 동일한 방법으로 리튬 이차 전지를 제조하였다. A lithium secondary battery was manufactured in the same manner as in Example 5, except that Li 4 Ti 5 O 12 of Comparative Examples 1 to 5 described in Table 1 were used as the anode active material.
실험예 1Experimental Example 1
<SEM 현미경 사진><SEM micrograph>
상기 비교예 3 및 실시예 1에서 제조된 리튬 금속 산화물 음극 활물질을 각각 SEM 현미경 사진으로 확인하였고, 그 결과를 각각 도 1 및 도 2에 나타내었다. The lithium metal oxide anode active materials prepared in Comparative Example 3 and Example 1 were confirmed by SEM micrographs, respectively, and the results are shown in FIGS. 1 and 2, respectively.
도 1은 평균 입경이 6.5 ㎛이고, 내부 공극률이 15 %인 Li4Ti5O12의 SEM 사진으로서, 일차 입자의 응집으로 인하여 상기 이차 입자에는 내부 및 표면에 공극이 형성된 다공질의 이차 입자임을 확인할 수 있다. 이때 입자 내부의 검은색 부분은 공극을 나타낸다.1 is an SEM image of Li 4 Ti 5 O 12 having an average particle diameter of 6.5 μm and an internal porosity of 15%. The secondary particles are porous secondary particles having pores formed on the inside and the surface thereof due to aggregation of the primary particles. Can be. At this time, the black part inside the particle represents a void.
한편 도 2의 경우, 일차 입자가 응집되어 이차 입자로 구성되어 있으며, 평균 입경이 5.4 ㎛이고, 내부 공극률이 3.5 %인 Li4Ti5O12의 SEM 사진으로서, 비교예 1의 Li4Ti5O12 보다 고밀도로 구성되어 있음을 육안으로 확인할 수 있다. In some cases, the second, the primary particles are agglomerated, and is composed of the secondary particles, and the average particle diameter of 5.4 ㎛, a SEM picture of the internal porosity of 3.5% of Li 4 Ti 5 O 12, Comparative Li 4 Ti 5 of Example 1 It can be seen visually that the composition is higher density than O 12 .
실험예 2Experimental Example 2
<접착력 측정><Adhesion measurement>
실시예 5 내지 8 및 비교예 6 내지 10의 리튬 이차 전지의 제조 과정 중 제조된 음극을 사용하여 음극에 대한 접착력 측정을 수행하였다. 접착력 측정은 일반적으로 알려진 180 o peel test로 진행하였다. 그 결과를 하기 표 2에 나타내었다.The adhesion to the negative electrode was measured using the negative electrode prepared during the manufacturing process of the lithium secondary battery of Examples 5 to 8 and Comparative Examples 6 to 10. Adhesion was measured by a commonly known 180 o peel test. The results are shown in Table 2 below.
<고율 특성 분석><High Rate Characteristic Analysis>
본 발명의 실시예 5 내지 8 및 비교예 6 내지 10의 리튬 이차 전지의 고율 특성 분석을 위해, 충방전 밀도를 각각 0.1, 0.2, 0.5, 1, 0.2, 2, 0.2, 5, 0.2, 10C로 순차적으로 진행하였다. 이때 충전 종지 전압은 1.0V이고, 방전 종지 전압은 2.5V로 설정하였다. 상기 고율 특성은 10C에서의 용량을 측정하여 0.1C에서의 용량 대비 백분율 값으로 나타낸 것이다. For high rate characterization of the lithium secondary batteries of Examples 5 to 8 and Comparative Examples 6 to 10 of the present invention, charge and discharge densities were set to 0.1, 0.2, 0.5, 1, 0.2, 2, 0.2, 5, 0.2, and 10C, respectively. It proceeded sequentially. At this time, the charge end voltage was set to 1.0V, and the discharge end voltage was set to 2.5V. The high rate characteristic is expressed as a percentage value of the capacity at 0.1C by measuring the capacity at 10C.
그 결과를 하기 표 2에 나타내었다.The results are shown in Table 2 below.
표 2
전극조성(활물질/도전재/바인더) 접착력(gf) 10C/0.1C(%)
실시예5 88/4/8 15 78
실시예6 88/4/8 12 74
실시예7 88/4/8 7 70
실시예8 88/4/8 20 72
비교예6 88/4/8 20 67
비교예7 88/4/8 4 66
비교예8 88/4/8 2 60
비교예9 88/4/8 6 63
비교예10 88/4/8 25 64
TABLE 2
Electrode composition (active material / conductive material / binder) Adhesive force (gf) 10C / 0.1C (%)
Example 5 88/4/8 15 78
Example 6 88/4/8 12 74
Example 7 88/4/8 7 70
Example 8 88/4/8 20 72
Comparative Example 6 88/4/8 20 67
Comparative Example 7 88/4/8 4 66
Comparative Example 8 88/4/8 2 60
Comparative Example 9 88/4/8 6 63
Comparative Example 10 88/4/8 25 64
하기 표 2에 나타낸 바와 같이, 유사한 Li4Ti5O12 입자의 평균 입경을 가지는 경우 리튬 금속 산화물 입자의 내부 공극률의 차이에 의해서 전극의 접착력의 차이가 있음을 확인하였으며, 더 나아가 고율 특성에 영향을 주는 것을 확인 할 수 있다. 이것은 리튬 금속 산화물 입자의 내부 공극률이 커지는 경우 리튬 금속 산화물 입자 내 공극에 바인더 물질이 들어가게 되어 음극 활물질과 도전재 간 연결이 느슨하게 되어 전극 저항이 증가하게 되고, 결국 고율 특성이 저하되는 결과가 나타난 것으로 이해할 수 있다. As shown in Table 2, when the average particle diameter of the similar Li 4 Ti 5 O 12 particles, it was confirmed that there is a difference in the adhesive strength of the electrode by the difference in the internal porosity of the lithium metal oxide particles, and further affect the high rate characteristics You can check what gives. This is because when the internal porosity of the lithium metal oxide particles increases, the binder material enters the voids in the lithium metal oxide particles, thereby loosening the connection between the negative electrode active material and the conductive material, thereby increasing the electrode resistance, resulting in a decrease in the high rate characteristic. I can understand.
또한 리튬 금속 산화물 입자의 내부 공극률이 너무 작은 경우 내부 활물질에 전해액 침투가 원활히 이루어지지 않아 높은 접착력을 가짐에도 불구하고 고율 특성이 저하되는 원인이 된다. In addition, when the internal porosity of the lithium metal oxide particles is too small, the electrolyte solution does not penetrate smoothly into the internal active material, which causes the high rate characteristics to deteriorate despite having a high adhesive force.
게다가, 유사한 내부 공극률을 가지는 리튬 금속 산화물 입자의 경우에도 이의 입경 차이에 의한 전극 접착력 및 고율 특성이 상이하게 나타나는 것이 확인되었으며, 입경이 너무 작은 경우에는 전극 접착력 저하에 의한 결과로 해석될 수 있다.In addition, even in the case of lithium metal oxide particles having a similar internal porosity, it was confirmed that the electrode adhesion and high rate characteristics due to the difference in the particle diameter is different, and when the particle diameter is too small, it can be interpreted as a result of the decrease in the electrode adhesion.
한편, 리튬 금속 산화물 입자의 입경이 큰 경우, 입자 내부의 활물질의 전기 전도성이 떨어지게 되어 고율 특성이 저하될 수 있음을 알 수 있다.On the other hand, when the particle diameter of the lithium metal oxide particles is large, it can be seen that the electrical conductivity of the active material inside the particles is lowered, whereby high rate characteristics may be reduced.
따라서, 고율 특성 향상을 위해서는 리튬 금속 산화물 입자의 내부 공극률 및 리튬 금속 산화물 입자의 평균 입경 간 조화가 필요함을 확인할 수 있다. Therefore, in order to improve the high rate characteristic, it can be seen that the harmony between the internal porosity of the lithium metal oxide particles and the average particle diameter of the lithium metal oxide particles is required.
상술한 바와 같이 본 발명의 기술적 사상에 의한 음극 활물질은 고밀도의 리튬 금속 산화물 입자를 포함함으로써 음극 접착력이 크게 향상될 수 있다. 이는 곧, 통상의 밀도를 갖는 종래의 음극 활물질에 비하여, 동일한 강도의 전극 접착력을 발휘하는 데에 필요한 바인더의 양을 현격하게 줄일 수 있다. As described above, the negative electrode active material according to the technical concept of the present invention may include a high density lithium metal oxide particle, thereby greatly improving the negative electrode adhesive force. This, in turn, can significantly reduce the amount of binder required to exert an electrode adhesive force of the same strength as compared with a conventional negative electrode active material having a normal density.
즉, 리튬 금속 산화물 입자의 내부 공극률이 감소됨에 따라, 리튬 금속 산화물 입자가 고밀도로 형성될 수 있다. 이러한 이유로 음극 슬러리의 제조시 필요한 바인더의 양을 감소시킬 수 있고, 나아가 이차 전지의 양산에 있어서 유리하다. That is, as the internal porosity of the lithium metal oxide particles is reduced, the lithium metal oxide particles may be formed at a high density. For this reason, the amount of binder required in the production of the negative electrode slurry can be reduced, and furthermore, it is advantageous in mass production of secondary batteries.
한편, 고밀도의 리튬 금속 산화물, 및 이로 인한 양호한 전극 접착력의 구현이 가능하기 때문에, 리튬 금속 산화물 입자의 평균 입경을 더욱 작게 형성하는 것이 가능하며, 이로 인하여 이차 전지의 고율 특성이 개선될 수 있다. On the other hand, since it is possible to implement a high density lithium metal oxide, and thereby good electrode adhesion, it is possible to form a smaller average particle diameter of the lithium metal oxide particles, thereby improving the high-rate characteristics of the secondary battery.

Claims (14)

  1. 리튬 금속 산화물 입자를 포함하고, Contains lithium metal oxide particles,
    상기 리튬 금속 산화물 입자의 내부 공극률은 3 % 내지 8 %이고, 평균 입경(D50)은 5 ㎛ 내지 12 ㎛인 것을 특징으로 하는 음극 활물질. The internal porosity of the lithium metal oxide particles is 3% to 8%, the average particle diameter (D 50 ) is a negative electrode active material, characterized in that 5 ㎛ to 12 ㎛.
  2. 제 1 항에 있어서, The method of claim 1,
    상기 리튬 금속 산화물은 LixMyOz (M은 각각 독립적으로 Ti, Sn, Cu, Pb, Sb, Zn, Fe, In, Al 또는 Zr로 이루어진 군에서 선택된 어느 하나 또는 이들 중 2 이상의 원소이고; x, y 및 z는 M의 산화수(oxidation number)에 따라 결정된다)로 표시되는 화합물인 것을 특징으로 하는 음극 활물질. The lithium metal oxide is Li x M y O z (M is independently any one selected from the group consisting of Ti, Sn, Cu, Pb, Sb, Zn, Fe, In, Al or Zr or two or more of these elements) x, y and z are determined according to the oxidation number of M).
  3. 제 1 항에 있어서, The method of claim 1,
    상기 리튬 금속 산화물은 Li4Ti5O12, LiTi2O4, Li2TiO3 및 Li2Ti3O7로 이루어진 군으로부터 선택되는 어느 하나 또는 이들 중 2종 이상의 혼합물인 것을 특징으로 하는 음극 활물질. The lithium metal oxide is any one selected from the group consisting of Li 4 Ti 5 O 12 , LiTi 2 O 4 , Li 2 TiO 3 and Li 2 Ti 3 O 7 or a mixture of two or more thereof. .
  4. 제 1 항에 있어서, The method of claim 1,
    상기 리튬 금속 산화물 입자는 둘 이상의 일차 입자가 응집된 이차 입자인 것을 특징으로 하는 음극 활물질.The lithium metal oxide particles are negative active material, characterized in that the secondary particles are agglomerated two or more primary particles.
  5. 제 4 항에 있어서, The method of claim 4, wherein
    상기 일차 입자의 평균 입경은 100 nm 내지 400 nm인 것을 특징으로 하는 음극 활물질. The negative electrode active material, characterized in that the average particle diameter of the primary particles is 100 nm to 400 nm.
  6. 제 1 항에 있어서, The method of claim 1,
    상기 리튬 금속 산화물 입자의 비표면적(BET)은 2 m2/g 내지 8 m2/g 인 것을 특징으로 하는 음극 활물질.The specific surface area (BET) of the lithium metal oxide particles is 2 m 2 / g to 8 m 2 / g negative electrode active material, characterized in that.
  7. 리튬염 및 금속 산화물을 휘발성 용매에 첨가 및 교반하여 전구체 용액을 제조하는 단계, Adding a lithium salt and a metal oxide to a volatile solvent and stirring to prepare a precursor solution,
    상기 전구체 용액을 분무건조 장비의 챔버 내로 공급하는 단계, Supplying the precursor solution into the chamber of the spray drying equipment,
    상기 전구체 용액을 상기 챔버 내에서 분무하여 건조하는 단계를 포함하는, 내부 공극률이 3 % 내지 8 %이고, 평균 입경(D50)이 5 ㎛ 내지 12 ㎛인 리튬 금속 산화물 입자의 제조방법.Spraying the precursor solution in the chamber and drying, the method of producing lithium metal oxide particles having an internal porosity of 3% to 8%, the average particle diameter (D 50 ) of 5 ㎛ to 12 ㎛.
  8. 제 7 항에 있어서, The method of claim 7, wherein
    상기 리튬염은 수산화 리튬, 산화 리튬 및 탄산 리튬으로 이루어진 군에서 선택된 어느 하나 또는 이들 중 2종 이상의 혼합물인 것을 특징으로 하는 리튬 금속 산화물 입자의 제조방법.The lithium salt is a method for producing lithium metal oxide particles, characterized in that any one selected from the group consisting of lithium hydroxide, lithium oxide and lithium carbonate or a mixture of two or more thereof.
  9. 제 7 항에 있어서, The method of claim 7, wherein
    상기 금속 산화물은 산화 티탄인 것을 특징으로 하는 리튬 금속 산화물 입자의 제조방법.The metal oxide is a method for producing lithium metal oxide particles, characterized in that the titanium oxide.
  10. 제 7 항에 있어서, The method of claim 7, wherein
    상기 휘발성 용매는 물, 알코올 또는 아세톤인 것을 특징으로 하는 리튬 금속 산화물 입자의 제조방법. The volatile solvent is water, alcohol or acetone manufacturing method of lithium metal oxide particles, characterized in that.
  11. 제 7 항에 있어서, The method of claim 7, wherein
    상기 챔버 내로의 상기 전구체 용액의 공급 속도는 10 ㎖/분 내지 1000 ㎖/분인 것을 특징으로 하는 리튬 금속 산화물 입자의 제조방법. The feed rate of the precursor solution into the chamber is a method of producing lithium metal oxide particles, characterized in that from 10 mL / min to 1000 mL / min.
  12. 제 7 항에 있어서, The method of claim 7, wherein
    상기 건조는 20 ℃ 내지 300 ℃의 온도에서 수행되는 것을 특징으로 하는 리튬 금속 산화물 입자의 제조방법. The drying is a method for producing lithium metal oxide particles, characterized in that carried out at a temperature of 20 ℃ to 300 ℃.
  13. 제 1 항에 따른 음극 활물질을 포함하는 것을 특징으로 하는 음극.A negative electrode comprising the negative electrode active material according to claim 1.
  14. 제 13 항에 따른 음극을 포함하는 것을 특징으로 하는 이차 전지.A secondary battery comprising the negative electrode according to claim 13.
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